Lubricating compositions



United States Patent 3,234,129 LUBRICATING COMPOSITIONS Warren L. Perilstein, Orchard Lake, Mich., assignor to Ethyl Corporation, New York, N.Y., a corporation of Virginia No Drawing. Filed Aug. 1, 1962, Ser. No. 213,900 4 Claims. (Cl. 252-32.7)

The present invention relates to lubricating composi tions containing as essential ingredients a tungsten compound and a sulfur-containing compound.

It is well known to deposit solid lubricating films on metal wear surfaces by a chemical process. These involve a reaction of the wear surface with its environment and thus there is a sacrificial loss of metal. In contradistinction to such a process, the present invention is concerned with the in situ formation of a tungsten film which, with the possible exception of catalytic action, does not involve a reaction with the metallic surface. More particularly, the present invention provides lubricating compositions containing two chemical species which due to temperatures and pressures generated by rubbing surfaces react intermolecularly to form a new species which provides the lubricating film.

It is known that solid oil-insoluble materials such as, for example, tungsten disulfide may be deposited on a metallic surface to form a laminar structure to enhance anti-friction and lubricant properties. Generally such coatings are obtained by forming a colloidal suspension of the tungsten compound in the oil (or grease). During running, the suspension is deposited on the metallic surface and fills the irregularities therein, thus reducing friction and improving wear and lubricating properties. However, such solutions suffer a disadvantage which is inherent with every colloidal suspension in that they are susceptible to flocculation which causes a loss of effectiveness.

It is the object of the present invention to provide lubricating compositions containing solutions of a tungsten compound and a sulfur-containing material. Another object is to providelubricating compositions wherein under the influence of temperatures and pressures generated by rubbing surfaces, two chemical speciesreact to form a third species. Another object is to provide lubricating compositions having superior antiwear and anti-friction properties. Still another object of the invention is to provide a method for the deposition of a tungsten-sulfur compound on metallic surfaces.

The objectives of this invention are accomplished by providing lubricant compositions prepared by dissolving in a lubricant, a soluble compound of tungsten and a soluble compound of sulfur. Under the influence of operating temperatures and pressure, i.e., during running,

the two constituents react to form a tungsten-sulfur prodnot. This latter material is then deposited on the metallic surfaces to be lubricated. The nature of the reaction product is complex and undefined; however, the electron defraction patterns obtained on the product show that W8 WO ,'WO and W O are not present.

As stated above there are two essential constituents in the lubricating composition of this invention-a tungsten compound-and a sulfur-containing compound. In order to be useful as additives of this invention, the compounds must be soluble in the lubricating medium, and must be capable of reacting to form a tungsten-sulfur product.

3,23%,l2 Patented Feb. 8, 1966 lCe One class of useable tungsten compounds are the arene tungsten tricarbonyls having the formula wherein R represents an aromatic compound having a benzene nucleus coordinated to the tungsten atom through the carbon atoms of the benzene ring. The carbonyl groups are electron donors and are involved in covalent and coordinate-covalent bonding with the tungsten atom. These compounds achieve stabilization through coordination of sufiicient electrons to give tungsten the configuration similar to that of the next higher rare gas. With these compounds the aromatic portion is actually a molecule as distinguished from an aryl radical such as phenyl, which is found in organometallic compounds. Each carbon of the aromatic ring is bonded, apparently by coordinate valences in a fashion such that the ring contributes 6 electrons to the metal atom. Likewise the carbonyl groups are also covalently or coordinatively bonded to the metal atom.

In the above formula R is an aromatic compound containing from 6 to about 15 carbon atoms. Examples of useable aromatic groups are benzene itself, mesitylene, toluene, biphenyl, tetralin, and the like. A preferred compound from this group is benzene tungsten tricarbonyl.

Another group of tungsten compounds useable in the present compositions are the bis-arene compounds of tungsten having the formula wherein R is an aromatic compound having up to about 15 carbon atoms. These compounds are aromatic complexes containing two 6-membered rings. Typical examples are dibenzene tungsten, dimesitylene tungsten, ditoluene tungsten, etc.

The arene tungsten tricarbonyls and the diarene tungsten compounds are known and methods for their preparation are described in organometallic Chemistry by H. Zeiss, Reinhold Publishing Corporation, New York, NY. (1960).

The preferred tungsten compounds used in the present compositions are those having the formula where R is an aryl radical having from 6 to about 18 carbon atoms and is preferably a phenyl or naphthyl radical and these radicals substituted with other hydrocarbon substituents such as alkyl and cycloalkyl radicals; X is chlorine or bromine and n is an integer from 1 to 6.

Typical examples of these tungsten compounds include tetrachlorodiphenoxy tungsten, dichlorotetraphenoxy tungsten, hexaphenoxy tungsten, hexa(m-tolyloxy)tung sten, hexa (3 ,5 -diethylphenoxy) tungsten, chloropenta lnaphthyloxy) tungsten, dichlorotetra( 1-naphthyloxy)tungsten, tetrachloro-di(2-naphthyloxy)tungsten, tetrachlorobis(4 methyl 1 napht-hoxy)tungsten, and hexa(lnaphthyloxy) tungsten.

The preferred compounds are those wherein all the halogen atoms are completely replaced by phenoxy or naphthyloxy groups, such as hexaphenoxy tungsten, hexa (1 naphthyloxy)tungsten, hexa(2,4 dipropylphenoxy) tungsten, and hexa(3,S-diethyl-l-naphthyloxy)tungsten.

One method for the preparation of this series of compounds involves reaction of tungsten hexachloride with the corresponding phenol or naphthol in the presence of a solventsuch ascarbon tetrachloride. The method is described by Funk and Baurnan, Z. Ano'rg. u. Allgem.Chem. 231, 264-266 (1937).

The second essential ingredient of the lubricantcompo-. sitions of this inventionis a soluble sulfur-containing com- 5 pound; Various classes of such compounds are the mer captans having the formula RSH; the sulfides, RSR and. the disulfides, RSSR; Wherein.;R and R are the same. or different and are hydrocarbon radicals containing. from 1 to about 30 carbon atoms and are selected from-the'group consisting of alkyl, cycloalkyl,;aryl, aralkyl, and alkaryl radicals. Alkyl and aryl radicals having up to about 12 carbon atoms are preferred.

The sulfur-containing compound'can also be a metal salt or an amine salt of substituted dithiocarbamic acids, or phosphorodithioic acids of the following formulae:

and

wherein R and R maybe-the same or different and are hydrocarbon radicals-of from 1 to about 30 carbon atoms selected from theagroup consistingof alkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicals. R and jR yare' pref+- erably alkyl radicals having froml toabout 12carbon atoms.

Any metal salt of the above enumerated acids which is soluble in thelubricating medium maybe used. #However, it is preferred to-employ metals from Groups I- A,-=IIA,- II-B, IV-A, V-A and VIII of the Periodic Table, especi-; ally cadmium, calcium, barium, nickel, sodium, lead, bismuth and. zinc.

The amines which may be employed tofornrsaltswith the above acidsinclude primary, secondary, and tertiary amines substituted withhydrocarbon radicals of from 1 to about 20 carbon atoms and are preferablyalkylor 40 cycloalkyl amines having from 2 toabout 12- carbon atoms in each hydrocarbon group.

Anoutstanding' embodiment of the u seable sulfur'com pounds are themetal dialkyl phosphorodithioates having the formula 5 wherein M is a divalent metal selectedfrom the group consisting-of=cadmium, barium, calcium, nickeland'zinc, and R is an alkyl radical containing from 1 toabout carbon atoms preferably 2 to 12'carbon atoms. Zinc is. i an especiallypreferred embodiment. These compounds, when used in combination with the above definedtung'sten compounds provide. lubricating. compositions without: standing wear and anti-frictionproperties.

The. ratio of the two essential in'gredientsof the' lubri-' eating compositions is not critical. However, itis'preferred to use fronrabout 0.2 to 10 partsof the metal complex perpart of the sulfur-containingcompound. .In 2. many applications a ratio 'of from '-about-0.'5:'1. to 2:1 is optimum.

The additives of this invention may each be-used in a a concentration of from about 0.005 to 5 weight percent. Dueeto the highly 'effective nature of the present additives, and because of economic considerations,concentration'of I from about 0.05 to about 1.0 percent of each of the essentialv ingredients is preferred, In many applications, concentrations as lowzas 0.1 to 0.2 percent are ioptimum. to impart the desired properties to the-lubricating com- 70 positions. a

In formulating the lubricating compositiohswithin thescope of this invention,'the base material may be any. lubricant known to'the a'rtu Thus, itmaybe .a hydrocarbon base material derived from sources-such as animal, 75

vegetable and mineraloil stock One preferred lubricant base is a mineialfoilfdefiv'ed"from crude .oil'stock and combinations of theabove reactants- One preferred eme. bodiment: of such synthetic I oils; are diesterj .oils obtained by reaction :of a dicarboxylic acid with a branched. chain alcohol such a as for example? between succinic acid with amyl alcohol.

Other synthetic oils that are useful as the base lubricant" include silicones, siloxanes,silanes, alkoXy silanes, aryloxy silahes, etc. Othersynthetic mateiials such as fluorocarbons may also be used..

soaps, may be :derived' from mineral or vegetable fats or fatty acids, wool grease, rosin or petroleum acids.

noun fillersu Some outstandingcompositions-of the present invention I are shown by thefollowing examples.

and the dibutyl sulfide; reactrto form -a:t1mgsten-sulfur product which is deposited on iwear surfacestherebyimproving lubricating and anti-friction properties.-

EXAMPLE 11 l.

A solvent extracted Pennsylvania bright stock having. a viscosityhin'dex of {105 and a viscosity ofr660fSUS at:

terialffor this example. T01 this mineral oil is adde'diOl'l perceintf otihexyl mercaptan, and 0.05 percent dibenzene tungsten. V

EXAMPLEE III I is l43' an'd'its specificgravity-( Fi /60 F.) is 0926.. To this die'ste'r' is added 3.0 percent ofthe saltj of dibutyl amine and dioctyl=phosphorodithioic acid. Also addedto the oil is -1'.0'weight ipercenttof: benzene tungsten .tri-" carbonyl.

EXAMPLE IV Y To Dow-Corning 200 silicone fluid is added 2.0 percent of the salt'of hexyl amine and diethyl; dithiocarbamic acid.

Alsotadded' to theibase fluid is 0.2 percent of-dibromotetraphenoxytungsten; Dow-Corning 200 siliofcne fluidis a dimethyl. polysilo'xane havin'g 1 8. vvi'scdsity j of l 'ce'nti stokes at 25, C2, an open cupfla'sh point of" 575 C.', a

pour point i'of --67 F., and a specific: gravity of 0970 i The greasemay also be "derivedfrom the synthetic lubricants discussed above with a soap and fwith or without addi- '5 EXAMPLE V" The base lubricant of this example is a grease consisting of 15 percent of soda soap prepared from equal amounts of stearic" acid and of rosin, percent candelill'a wax and 75 percent of minerallubricating oil of aviscosity of 100 SUS at 210 F. and a'viscosity index of 72. To this grease are added 4 percent of the cadmium salt-of dihexyl dithiocarbonic acid. Also added to the grease is 5.0 percent of dichlorotetra(Z-naphthyloxy) tungsten.

EXAMPLE VI Wear Testing Machine to measure the wear properties of various lubricating compositions. The machine is described by Larsen and Perry in the Transactions of the A. S .M.E., January 1945, pages 45-50. It operatesin therangeof 0.1 to '50 kilograms.

The machine utilizes four balls of equal size arranged in a tetrahedral formation. The bottom three balls are held in a non-rotatable fixture which is essentially a universal chuck that holds the balls in abutting relation to each other. Since the bottom three balls are of equal size, their centers form the apices of an equilateral triangle. The top ball is affixed to a rotatable spindle whose axis is positioned perpendicularly to the plane of the ball holder and in line with the center point of the triangle, whose apices are the centers of the three bottom stationary balls.

In operation, the four balls are immersed in the lubricant composition to be tested, and the fixture holding the three bottom balls is moved upwardly so as to bring the three fixed lower balls into engagement with the upper rotating ball. As the load is increased, the fixture is moved upwardly and axial of the rotating spindle affixed to the upper ball.

The lubricity of the lubricant under test and, therefore, the anti-wear activity of the additive it contains, is determined by the amount of wear occurring on the lower balls at the points of contact with the upper rotating ball. If the lubricant is completely effective, the amount of wear will be negligible. On the other hand, if the lubricant is not completely effective under the test conditions, the wear which occurs on the lower three balls will be excessive. The average diameter of the circular scar areas of the lower balls is measured so as to give a quantitative basis for comparing the test results with those of other tests. The smaller the scar diameter, the more effective is the additive as an anti-wear agent.

Various lubricating compositions were subjected to the Four Ball Wear test to determine the lubricating effectiveness of the compositions of this invention as compared to a non-additive-containing base lubricating medium. The test conditions were the same in each of the tests with the four balls being /2" in diameter and constructed of SAW 52100 steel. The speed of rotation of the upper ball was 1800 r.p.m. and the lubricant was maintained constant at 125 C. Tests were carried out at a loading of 50 kilograms.

In order to establish a base line for comparison, a nonadditive-containing paraffinic white mineral oil having a viscosity of 17.15 centistokes at 100 F. and 3.64 centistokes at 210 F., and a viscosity index of 107.5 was tested. Also tested were samples of the mineral oil-containing tungsten compound or a sulfur-containing ma- '6 terial. Compositions of this invention wherein the mineral oil contained both atungsten compound and a sulfurcontaining material were also tested. Wear, in terms of scar diameter, wasmeasured periodically. Typical results of these testsare set forth in the following table in which the values for scar'diameters are average values obtained from a number'of runs.

Table I WEAR PnorEnT rEsor"vanious LUB'RICATTNG COM- POSITIONS Sear diameter, mm.

+0.1% P as Mixture of zincdipropyl, dibutyl anddih'exyl phosphorodithioate.

" The" zinc dialkyl phosphorodithioate' improved the lubri- *catingproperties to a degree, but became less efiective during the latter part of the test. For example, after 300 minutesof running, scar diameters of 1.97 mm. obtained with the base lubricant'were not reduced by adding the tungsten compound, and. only reduced to 1.0 mm. by addition of the zinc compound.

Unexpectedly, the lubricant containing both the tungsten compound and the sulfur compound showed a remarkable improvement in wear properties as evidenced by a scar diameter of only 0.40 mm. after 300 minutes of running. Thus, there is clearly an interaction between the two compounds to form a third species with lubricating properties, greater than would be expected from a knowledge of the etfectiveness of each component. Similar results are obtained with other compositions of this invention.

The lubricants of this invention can also contain other additives used to impart desirable characteristics to the base. By way of example, the lubricants can contain detergent-dispersants such as barium and calcium sulfonates, or naphthenates, polymethacrylates, reaction products of dibasic acids with amines such as alkenyl succinimides, rust inhibitors such as dibasic acids and their anhydrides and irnides and amides of these acids, antioxidants such as phenylene diamine, and hindered phenols such as 2,6-di-tert-butyl-4-methyl phenol, 4,4'-mcthylene bis(2,6-di-tert-butyl phenol), etc. The present composition may also contain viscosity index improvers such as polymerized olefins or isoolefins, butylene polymers, methacrylic acid ester polymers, alkylated styrene polymers, color stabilizers such as hydroquinones, dithiocarbamates, aliphatic amines, dicyclohexyl amines, etc.

I claim.

1. A lubricant composition comprising a major proportion of a lubricant base selected from the class consisting of hydrocarbon base lubricating oils and greases and synthetic base lubricating oils and greases containing:

(A) from 0.005 to about 5 per cent of a tungsten compound selected from the group consisting of (1) diarene tungsten compounds wherein each arene moiety is an arene hydrocarbon moiety of 6 to about 15 carbon atoms (2) arene tungsten tricarbonyl compounds wherein said arene moiety is an arene hydrocarbon moiety of 6 to about 15 carbon atoms the metal in said salts being selected from 7 1ft" dd'btld'ldfi the class cons1st1ng of the metals'of Groups Su ur con ammg compoun 1S 1 u y lsu fi e 3 P V if a References Cited by the Examiner l erio 1c a e, an e amine 1n sai 's i being selected fromfthe-class consisting of UNITED S PATENTS primary, secondary and tertiary amines 2,609,342 9/1952 Whiteet a1. 252 -25 substituted with hydrocarbon radicals :of 3,047,500 7/1962 Maison V 252-46'.4 from one to about 20 carbon atoms 30 FQREIGN PATENTS wherein R and R may be the same or dif-" ferent and are hydrocarbon radicals having 844,811 8/1960 Great f l from 1 to about 30 carbon atoms selected. 865,970 4/1961- Great Bmamfrom the group consisting of alkyl, cyclo p a a I ,alkyl aryl alkaryl and aralkyl radica1s 35v DANIELE. WYMAN, Primary Examiner.

7 8i: (3-) compounds having the formula 2.2The composition of'claim 1 wherein said tungsten wxsmwmn compound has the formula where R is an aryl radical selected from the W(OR.)@ group consisting of phenyl and naphthyl radwherein R is an aryl radical selectedfrom the group conicals; X is selected from the group consisting sistingof phenyl and naphthyl radicals and these radicals of chlorine and bromine, and n is an eg substituted with other hydrocarbon substituents so that from 1 to 6, and said aryl radical containsv from 6 'tovabout 18 carbon (B) from 0.005 to about 5 per cent of a sulfur-conatoms, and said sulfurvcontaining compound has the form- I taining compound selected from the group consisting 10 ula (1) mercaptans of the formula RSH fi (2) sulfides of the formula RSR M*[S P (O (3) di lfid f th f l RSSR wherein M is a bivalent metal selected from the group (4) i1- 1ub1 t l d amine n f cids 15 consisting of cadmium, calcium, barium,'nickel,' and-zinc, having the formulae and R is an :alkyl group having from about 1 to 12 carbon (3) R S atoms.

7 3. iThe-composition of claim 2 wherein saidtungsten compound is hexanaphthyloxy tungsten andsaid sulfur- B1 SH containing compound, is'ra zinc dialkyl phosphorodithi- (b) s oate.

(ROMIILSH 4.5The-composition of claim 2 wherein said-tungsten compound is .dichlorotetranaphthyloxy :tungsten :and said 

1. A LUBRICANT COMPOSITION COMPRISING A MAJOR PROPORTION OF A LUBRICANT BASE SELECTED FROM THE CLASS CONSITING OF HYDROCARBON BASE LUBRICATING OILS AND GREASES AND SYNTHETIC BASE LUBRICATING OILS AND GREASEES CONTAINING: (A) FROM 0.005 TO ABOUT 5 PER CENT OF A TUNGSTEN COMPOUND SELECTED FROM THE GROUP CONSISTING OF (1) DIARENE TUNGSTEN COMPOUNDS WHEREIN EACH ARENE MOIETY IS AN ARENE HYDROCARBON MOIETY OF 6 TO ABOUT 15 CARBON ATOMS (2) ARENE TUNGSTEN TRICARBONYL COMPOUNDS WHEREIN SAID ARENE MOIETY IS AN ARENE HYDROCARBON MOIETY OF 6 TO ABOUT 15 CARBON ATOMS (3) COMPOUNDS HAVING THE FORMULA 